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Bio-Inspired Crystallization of Oxide Compounds Within Inorganic Matrices

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Bio-Inspired Crystallization of Oxide Compounds Within Inorganic Matrices BIO-INSPIRED CRYSTALLIZATION OF OXIDE COMPOUNDS WITHIN INORGANIC MATRICES A Dissertation Presented to the Faculty of the Graduate School of Cornell University In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy by Emily Asenath Smith May 2015 © 2015 Emily Asenath Smith BIO-INSPIRED CRYSTALLIZATION OF OXIDE COMPOUNDS WITHIN INORGANIC MATRICES Emily Asenath Smith, Ph. D. Cornell University 2015 The energy crisis facing our planet requires solutions that take an interdisciplinary approach to the improvement of existing energy systems as well as the development of new energy sources. Moreover, the composition of the materials is important: thermally- and chemically-stable materials based on abundant, non-toxic elements are needed to support the sustainability of both the technology and our environment. Biological organisms present multiple examples of hierarchical structures that are optimized for a given function. In particular, biomineralized materials: (i) display crystallographic control across length scales; (ii) are often organic-inorganic composites due to the occlusion of components from the associated organic growth matrix; (iii) and exhibit tailored mechanical properties that are unique to their function. Of great importance to the development of advanced energy materials is the observation that biomineral architectures are built from crystallographically-defined structural elements with interfaces that span multiple length scales. Synthetically, the translation of biological mineralization strategies to oxide compounds is hindered by the low melting temperatures of biopolymer hydrogels that compose extracellular matrices. In order to successfully crystallize oxide compounds using a (bio-inspired) matrix-mediated approach, I had to identify and develop a hydrogel system with thermal stability and chemical compatibility to the growth conditions needed for the oxide. By moving to inorganic networks based on silica, I achieved a thermally-stable growth matrix. By forming these networks at low pH, I obtained a growth environment that was compatible with the crystallization of hematite. With these two features, hematite was crystallized under diffusion-limited conditions, which provided a means to to manipulate its structure and assembly from the atomic- to the microscale. By combining inductively coupled plasma atomic emission spectroscopy with Rietveld refinements to x-ray diffraction data, expansion of the hematite lattice along the c-axis was found to be correlated to increasing silicon in the crystals and the preferential growth of the coherent domains along [110] (perpendicular to the strained c-axis). Using single particle manipulation in a focused ion beam system, electron-transparent thin sections were prepared from precisely-defined geometric locations within the hematite crystals for analysis by transmission electron microscopy. Quantitative analysis on selected area electron diffraction patterns was used to unravel the net orientation of the hematite lattice with respect to the quasi-spherical form and to calculate the misorientation (mosaicity) between the coherent domains. The combined results of these analyses showed that silicon from the growth environment had consistently modified the architecture of hematite, from the atomic to the microscale, leading to microscale structures with surfaces composed of nanoscale, high catalytic activity {110} facets. With hydrogel growth as a demonstrated route to tune the hierarchical structure of a transition metal oxide to preferentially express desired planes, the bandgap and photocatalytic activity of the samples was studied, to reveal that these micro-scale hierarchical architectures outperform their nano-sized counterparts, presenting a new approach to the design of materials for advanced energy applications. BIOGRAPHICAL SKETCH iii ACKNOWLEDGEMENTS Few would argue that completing a PhD is a major undertaking that requires commitment and perseverance. I would argue that the PhD itself is not the biggest challenge; it is all those other ‘things’ that occur while completing the PhD that introduce most difficult complexities. As an example, consider having a middle school social studies project that is due the day of your qualifying exam. Then, imagine hosting a proper tea party for a girl’s birthday celebration (complete with authentic Genoise Petits Fours) when you are only home for 48 h in a 10 d period. Next try to visualize yourself working through the geometry of arcs and cords via Skype after a 12 h day running experiments in 3 different labs. Finally, visualize mentoring a special education student on an electrical engineering science fair project and report that is to be on display the day your thesis is due. How is a PhD candidate to handle such challenges with grace and patience?! It is only with a multi-dimensional support network (of course!) that I have been able to balance all of these ‘things’ while completing my PhD with a normal timeline –and somewhere along the way, I have still found time to take care of myself. The foundation of my support network is held together by my husband –I must express my sincerest gratitude and appreciation to him for being my champion partner in this high-stakes high- rewards life we have together. I am so very grateful for my children, whose interests and understandings are my strongest motivators throughout my educational pursuits. Thank you to Tahquiy, for making me a better mathematician. Thank you to Jaleal for helping me to use electrical engineering skills I didn’t know I had! Thank you to Natiqua for always being excited to try new things; whether it is knitting or cooking, softball or growing crystals, you are always smiling. I appreciate my mother and my sister for supporting my decisions and understanding that physical distance is no measure of love. I honor my grandparents for the value that they put on education and the example that they set in developing their careers and growing their family simultaneously. I want to acknowledge financial support from the National Science Foundation through the Graduate Research Fellowship and IGERT Programs. These sources of independent funding both helped iv me to support my family during my graduate studies and enabled me to personally design my own thesis and those of multiple undergraduate researchers. It allowed me the flexibility that I needed to pursue new research directions and grow as a mentor. I want to specifically acknowledge Prof. Wei Chen, my research advisor at Mount Holyoke College, for encouraging me to pursue a PhD and fostering my ability to secure funding to support it. In the academic realm, I am thankful to my advisor, Prof. Lara Estroff, for allowing me the independence to design my own thesis and those of many others. Thank you to Lara for prioritizing my initiative to international research experiences. Thank you for supporting my involvement in research collaborations. I am grateful to my committee members, Prof. Frank DiSalvo and Prof. Sol Gruner, for providing me with new perspectives on research and supporting my career development. I am also grateful to Prof. Lena Kourkoutis for bolstering my ability to communicate across disciplines. I greatly appreciate friends and colleagues that have been my steadfast mentors in this long journey. Francie Viggiani and Linda Jones have consistently guided my professional development and given me the right balance of thoughtful guidance and firm direction. Thank you to Jim DeYoreo for mentorship in research and career development. Thank you to Jason Dorvee for a mutually beneficial mentoring relationship that will surely stand the test of time. Thank you to Sarah Sadowska for helping me to define and articulate my goals for my career. My network of colleagues has grown immensely throughout my graduate studies. I want to specifically acknowledge the A-team –for a bit of humor and social engagement within the framework of top flight research. I am thankful for the members of the Estroff Research Group –what a diversity of interests and personalities we all have. I appreciate what a complimentary set we represent. I am grateful to members of the Wiesner, DiSalvo and Abruna groups for sharing their facilities and guidance as I carried out what often turned out to be unusual experiments. I am grateful to the Kourkoutis and Muller groups for their openness to guide my development as a microscopist and their willingness to collaboration. v During my PhD, I have been involved in numerous collaborations, domestic and international. Specifically, I want to acknowledge Derk Joester and his students, Lyle Gordon and Michael Cohen, for their tireless efforts working with me to bring atom probe tomography to any crystal that I can make. I am indebted to Prof. Fiona Meldrum and her research group for a lively collaboration on crystallization in confinement and for warmly welcoming my visits and those of my undergraduates to Leeds. More than anything else, I chose to undertake my PhD at Cornell University because of the Shared Facilities and their highly-skilled managerial staff. John Grazul and Mick Thomas are the perfect dynamic duo to any challenge that I have faced both in electron microscopy and in my personal life. Thank you, Thank you for caring so much about your users and the equipment. I am also grateful to Maura Weathers for running a great x-ray facility and freely sharing ideas to get the information I sought. No support network would be complete without the involvement of
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